Metallocene catalysts for olefin or styrene polymerization and polymerization method using the metallocene catalysts

ABSTRACT

The new metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene compound is a transition metal compound which a transition metal is coordinated with a main ligand such as cycloalkanedienyl group and an ancillary ligand. The functional groups of the compound having at least two functional groups are selected from the group consisting of a hydroxy group, a thiol group, a primary amine group, a secondary amine group, etc. The metallocene catalysts according to the present invention have a structure which an ancillary ligand of a metallocene compound is bonded with functional groups. A structure of the metallocene catalysts can be varied according to the metallocene compounds, the compound having at least two functional groups, and the molar ratio of each reactant. The metallocene catalyst is employed with a co-catalyst for styrene and olefin polymerization. The co-catalyst is an organometallic compound and a mixture of non-coordinated Lewis acid and alkylaluminium. The organometallic compound is usually alkylaluminoxane and organoaluminium compound. The syndiotactic polystyrenes and the polyolefins having good physical properties are prepared by using the metallocene catalyst according to the present invention. A monomer for polymerization includes styrene, derivatives of styrene, and a compound having ethylenically unsaturated double bonds. Those compounds are homopolymerized and copolymerized to give polystyrene and polyolefin.

FIELD OF THE INVENTION

The present invention relates to new metallocene catalysts for use inpreparation of olefin or styrene polymers and polymerization methodsusing the metallocene catalysts. More specifically, the presentinvention relates to new metallocene catalysts which are capable ofpreparing olefin or styrene polymers having a high activity, a goodstereoregularity, a high melting point, and a good molecular weightdistribution in the presence of a small amount of a co-catalyst. Thepresent invention also relates to polymerization method for preparingsuch olefin or styrene polymers using the metallocene catalysts.

BACKGROUND OF THE INVENTION

Olefin or styrene polymers are generally prepared by radicalpolymerization, ionic polymerization, or coordination polymerizationusing a Ziegler-Natta catalyst. Radical or ionic polymerization providesolefin or styrene polymers having mainly an atactic structure.Coordination polymerization using a Ziegler-Natta catalyst providesolefin or styrene polymers having mainly an isotactic structure.

The polymers are structurally divided into three groups such as atacticpolymers, isotactic polymers, and syndiotactic polymers, depending, onthe position of benzene rings as a side chain in relation to a mainchain of molecular structure of the polymers. An atactic structure meansthat configuration of side chains is irregular. An isotactic structuremeans that side chains are positioned at one side relative to a mainchain. A syndiotactic structure means that side chains are alternativelyarranged for a main chain.

The polymers having a syndiotactic structure have been onlytheoretically known, and practically not prepared until a metallocenecatalyst was employed to the preparation methods.

Development of the metallocene catalysts was to provide a syndiotacticpolystyrene having a stereoregularity or polyolefins having improvedphysical properties. The conventional metallocene catalysts have astructure which a Group IV transition metal compound of the PeriodicTable of Elements is coordinated with ligands composed of one or twocycloalkanedienyl groups or their derivatives. The Group IV transition bmetal of the Periodic Table of Elements contain titanium, zirconium,hafnium, etc. The cycloalkanedienyl groups include a cyclopentadienylgroup, an indenyl group, a fluorenyl group, etc.

The metallocene catalysts are usually employed with a co-catalyst. Theconventionally used Ziegler-Natta catalysts system is composed of ahalogenated titanium compound as a main catalyst and alkylaluminium as aco-catalyst. Example of the halogenated titanium compound is titaniumtetrachloride. Example of alkylaluminium is trimethylaluminium andtriethylaluminium.

While, recently developed metallocene catalyst system is employed withalkylaluminoxane as a co-catalyst, which is capable of preparingpolystyrenes having a stereoregularity or polyolefins having improvedphysical properties. Alkylaluminoxane is produced by reactingalkylaluminium with H₂O. Especially, syndiotactic polystyrene has astructure which benzene rings as a side chain is alternativelypositioned relative to a main chain of the polymer The syndiotacticpolystyrene has an excellent heat-resistance and physical propertiessince the polymer has about 270° C. of a melting point (T_(m)) due tostereoregularity comparing with the conventional amorphous atacticpolystyrene, which is of interest.

European Patent Publication No. 210 615 A2 (1987) discloses asyndiotactic polystyrene having a stereoregularity. Also, the patentdiscloses cyclopentadienyltitanium trichloride and an alkyl-substitutedcyclopentadienyltitanium trichloride such aspentamethylcyclopentadienyltitanium trichloride to prepare syndiotacticpolystyrenes. It is known that the metallocene catalysts have a goodactivity, molecular weight distribution, and syndiotactic index.

U.S. Pat. No. 4,544,762 discloses a preparation method of aluminoxanewhich can be used as a component of catalysts in the preparation ofhighly active and homogeneous Ziegler-Natta catalysts.

U.S. Pat. No. 5,026,798 discloses a process for polymerizing α-olefinswhich utilize certain monocyclopentadienyl metal compounds of a GroupIVb transition metal of the Periodic Table of Elements in an aluminoxaneactivated catalyst system to produce crystalline poly-α-olefins.

U.S. Pat. Nos. 08/844,109 and 08/844,110 disclose a new alkyl bridgedbinuclear metallocene catalyst (ABBM), silyl bridged binuclearmetallocene catalyst (SBBM), and alkyl-silyl bridged binuclearmetallocene catalyst (A-SBBM) for preparing a syndiotactic polystyrenehaving a high activity, a good stereoregularity, a high melting point,and a good molecular weight distribution.

Accordingly, the present inventors have developed new metallocenecatalysts for use in preparation of olefin or styrene polymers andpolymerization methods for effectively preparing such olefin or styrenepolymers using the metallocene catalysts.

OBJECTS OF THE INVENTION

An object of the present invention is to provide metallocene catalystswhich are capable of preparing olefin or styrene polymers having a highactivity, a good stereoregularity, a high melting point, and a goodmolecular weight distribution.

Another object of the present invention is to provide highly activemetallocene catalysts which are capable of preparing a large amount ofolefin or styrene polymers in the presence of a small amount of aco-catalyst.

A further object of the present invention is to provide preparationmethods of metallocene catalyst and polymerization methods foreffectively preparing olefin or styrene polymers using the metallocenecatalysts.

Other objects and advantages of this invention will be apparent from theensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

The new metallocene catalysts according to the present invention areprepared by reacting a metallocene compound with a compound having atleast two functional groups. The metallocene compound is a transitionmetal compound which a transition metal is coordinated with a mainligand such as cycloalkanedienyl group and an ancillary ligand.Functional groups in the compound having at least two functional groupsare selected from the group consisting of a hydroxy group, a thiolgroup, a primary amine group, a secondary amine group, etc.

The metallocene catalysts of the present invention can be prepared byreacting a metallocene compound with a dianion compound produced byreacting an alkali metal compound with a compound having thosefunctional groups.

The metallocene catalysts according to the present invention have astructure which an ancillary ligand of a metallocene compound is bondedto the functional groups of a compound having at least two functionalgroups. A structure of the metallocene catalysts can be varied accordingto the type of metallocene compounds, the type of the compound having atleast two functional groups, and the molar ratio of each reactant.

The metallocene catalyst is employed with a co-catalyst for styrene orolefin polymerization. The co-catalyst is an organometallic compound ora mixture of non-coordinated Lewis acid and alkylaluminium as it iswidely known. The organometallic compound is usually alkylaluminoxane ororganoaluminium compound.

The syndiotactic polystyrenes or polyolefins having high physicalproperties are prepared by using the catalyst system composed of ametallocene catalyst according to the present invention and aco-catalyst. The monomers for polymerization include styrene, styrenederivatives, or a compound having ethylenically unsaturated doublebonds. Those compounds are homopolymerized or copolymerized to givepolystyrene or polyolefin having a high activity, a goodstereoregularity, a high melting point, and a good molecular weightdistribution.

DETAILED DESCRIPTION OF THE INVENTION

The metallocene catalyst according to the present invention is preparedby reacting a metallocene compound with a compound having at least twofunctional groups. The metallocene catalyst has a structure which anancillary ligand of a metallocene compound is coordinated with afunctional group of a compound having at least two functional groups.

The metallocene compound of the present invention is represented by thefollowing general formulae (A) or (B). The compound having at least twofunctional groups is represented by the following general formulae (C),(D), or (E).

MR¹ _(a)R² _(b)R³ _(c)R⁴ _(4−(a+b+c))  (A)

MR¹ _(d)R² _(e)R³ _(3−(d+e))  (B)

T²—YR⁵Y′—T¹  (C)

wherein M in the formulae (A) and (B) represents a transition metal of aGroup IV, V or VI of the Periodic Table and preferably of a Group IVsuch as titanium, zirconium or hafnium; R¹, R², R³ and R⁴ arerespectively a hydrogen atom; a halogen atom; an alkyl group, acycloalkyl group or an alkoxy group of C₁₋₂₀; an aryl group, an aylarylgroup or an arylalkyl group of C₆₋₂₀; a cyclopentadienyl group; asubstituted cyclopentadienyl group; an indenyl group; a substitutedindenyl group; a fluorenyl group; or a substituted fluorenyl group; a, band c are respectively an integer of 0 to 4; and d and e arerespectively an integer of 0 to 3.

T¹, T², T³ and T⁴ in the formulae (C), (D) and (E) respectivelyrepresent a hydrogen atom; an alkyl group, a cycloalkyl group or analkoxy group of C₁₋₂₀; an aryl group, an alkylaryl group or an arylalkylgroup of C₆₋₂₀; or an alkali metal such as Na, Li, K, etc.; Y, Y′, Y″and Y′″ are respectively O, S, —Nr¹⁷ or —Pr¹⁸ (wherein r¹⁷ and r¹⁸ arerespectively an hydrogen atom; an alkyl group, a cycloalkyl group or analkoxy group of C_(1˜10); or an aryl group, an alkylaryl group or anarylalkyl group of C₆₋₂₀); R⁵, R⁶, R⁷ and R⁸ are respectively R′,R′—m—R″ or

(wherein R′, R″, R″′ and R″″ are respectively a linear alkyl group or abranched alkyl group of C_(6˜20); a cycloalkyl group or a substitutedcycloalkyl group of C_(3˜20); or an aryl group, an alkylaryl group or anarylalkyl group of C_(6˜40); r¹⁹ is a hydrogen atom; an alkyl group, acycloalkyl group or an alkoxy group of C_(1˜10); or an aryl group, analkylaryl group or an arylalkyl group of C₆₋₂₀); and m is an oxygenatom, a sulfur atom, —Nr¹⁷, —Pr¹⁸ or Sir¹⁷r¹⁸ (wherein r¹⁷ and r¹⁸ arerespectively a hydrogen atom; an alkyl group, a cycloalkyl group or analkoxy group of C₁₋₁₀; or an aryl group, an alkylaryl group or anarylalkyl group of C_(6˜20));

Q is N or —Cr²⁰ (r²⁰ is an alkyl group, a cycloalkyl group or an alkoxygroup of C_(1˜10); or an aryl group, an alkylaryl group or an arylalkylgroup of C_(6˜20)); and

Z is C, Si, Ge or

The representative examples of the metallocene catalysts according tothe present invention are represented by the following general formulae(I )˜(V):

wherein M, M′, M″ and M″′ in the general formulae (I)˜(V) arerespectively a transition metal of a Group IV, V, or VI of the PeriodicTable and preferably of a Group IV such as titanium, zirconium orhafnium;

Cp, Cp′, Cp″ and Cp″′ are respectively a cyclopentadienyl group, anindenyl group, a fluorenyl group or a derivative of each group whichforms η⁵-bond with a transition metal such as M, M′, M″ and M″′, also,Cp, Cp′, Cp″ and Cp″′ are represented by the general formulae (a), (b),(c) or (d);

(wherein r¹, r², r³, r⁴, r⁵, r⁶, r⁷, r⁸, r⁹, r¹⁰, r¹¹, r¹², r¹³, r¹⁴,r¹⁵, and r¹⁶ are respectively a hydrogen atom; an alkyl group, acycloalkyl group or an alkoxy group of C_(1˜20); or an aryl group, analkylaryl group or an arylalkyl group of C_(1˜20); and f is an integerof 4 to 8.)

X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, X⁹, X¹⁰, X¹¹, and X¹² are respectively ahydrogen atom; a hydroxy group; a halogen atom; an alkyl group, acycloalkyl group or an alkoxy group of C_(1˜20); or an aryl group, analkylaryl group or an arylalkyl group of C_(6˜40);

G, G′ and G″ are the groups connecting between two transition metals andare represented as —YR⁵Y′— or T²—YR⁵Y′—T¹ (wherein T¹ and T² representrespectively a hydrogen atom; and alkyl group, a cycloalkyl group or analkoxy group of C₁₋₂₀; or an aryl group, an alkylaryl group or anarylalkyl group of C₆₋₂₀);

Y, Y′, Y″ and Y″′ are respectively O, S, —Nr¹⁷ or —Pr¹⁸ (wherein r¹⁷ andr¹⁸ are respectively a hydrogen atom; an alkyl group, a cycloalkyl groupor an alkoxy group of C₁₋₁₀; or an aryl group, an alkylaryl group or anarylalkyl group of C₆₋₂₀); and R⁵ is R′, R′—m—R″ or

(wherein R′, R′, R″′ and R″″ are respectively a linear alkyl group or abranched alkyl group of C₆₋₂₀; a cycloalkyl group or a substitutedcycloalkyl group of C₃₋₂₀; or an aryl group, an alkylaryl group or anarylalkyl group of C₆₋₄₀; and m is an oxygen atom, a sulfur atom, —Nr¹⁷,—Pr¹⁸ or Sir¹⁷r¹⁸ (wherein r¹⁷ and r¹⁸ are respectively a hydrogen atom;or an alkyl group, a cycloalkyl group or an alkoxy group of C₁₋₁₀; or anaryl group, an alkylaryl group or an arylalkyl group of C₆₋₂₀));

Q is N or —Cr²⁰ (wherein r²⁰ is a hydrogen atom; an alkyl group, acycloalkyl group or an alkoxy group of C_(1˜10); or an aryl group, analkylaryl group or an arylalkyl group of C_(6˜20)); and

Z is C, Si, Ge or

A metallocene compound used for preparing the metallocene catalystaccording to the present invention is commercially available. Also, themetallocene compound may be prepared according to a method which isconventionally well known. The metallocene compound can be prepared bythe steps comprising; preparing a salt of a substituted cyclopentadienylligand containing alkali metal by reacting the correspondingcyclopentadienyl ligand with an alkali metal or an alkali metalcompound, introducing a silicon compound or tin compound to the salt ofa substituted cyclopentadienyl ligand, and reacting the above resultantcompound with a Group IV transition metal compound.

In case of substituting an ancillary ligand of a metallocene compoundwith an alkoxy group, an alkyl group, or any other groups, themetallocene compound is reacted with the desired equivalent of alcoholor alkyl metal compound. The above-described method for preparing ametallocene compound may be easily performed by an ordinary skilledperson in the art.

The alkali metals or alkali metal compounds include K, Na,η-butyllithium, secbutyflithium, tert-butyllithium, methyllithium,sodium methoxide, sodium ethoxide, etc.

The Group IV transition metal compound of the Periodic Table of Elementsinclude titanium tetrachloride, zirconium tetrachloride, and hafniumtetrachloride.

The representative examples of the metallocene compound represented bythe general formula (A) or (B) include:pepentamethylcyclopentadienyltitanium trichloride,pentamethylcyclopentadienyisethoxytitanium dichiide,pentamethylcyclopentadienyldimethoxytitanium monochloride,1,2,3,4-tetrarethylcyclopentadienyltitanium trichloride,1,2,3,4-tetramethylcyclopentadienylmethoxytitanium dichloride,1,2,3,4-tetramethylcyclopentadienyldimethoxytitanium monochloride,1,2,4-trimethylcyclopentadienylti tanium trichloride,1,2,4-trimethylcyclopentadienylrnethoxytitanium dichloride,1,2,4-trimethylcyclopentadienyldimethoxytitanium monochloride,1,2,-dimethylcyclopentadienyltitanium trichioride,1,2,-dimethylcyclopentadienylmethoxytitanium dichioride,1,2,-dimethylcyclopentadienyldimethoxytitanium monochloride,methylcyclopentadienyltitanium trichioride,methylcyclopentadienylmethoxytitanium dichioride,methylcyclopentadienyldimethoxytitanium monochloride,cyclopentadienyltitanium trichloride, cyclopentadienylmethoxytitaniumdichloride, cyclopentadienyldimethoxytitanium monochlonrde,pentamethylcyclopentadienylnethyltitanium dichloride,pentamethylcyclopentadienyldimethyltitanium monochloride,1,2,3,4-tetramethylcyclopentadienyhnethyltitanium dichloride,1,2,3,4-tetramethylcyclopentadienyldimethyltitanium monochloride,1,2,4-trimethylcyclopentadienylmnethyltitanium dichlonide,1,2,4-trimethylcyclopentadienyldimethyltitanium monochloride,1,2-dimethylcyclopentadienylmethyltitanium dichlonide,1,2-dimethylcyclopentadienyldimethyltitanium monochloride,methylcyclopentadienyhnethyltitanium dichloride,methylcyclopentadienyldimethyltitanium monochloride,cyclopentadienylmethyltitanium dichloride, andcyclopentadienyldimethyltitanium monochloride.

The representative examples of the compound having at least twofunctional groups represented by the general formulae (C), (D) or (E)include: ethylene glycol, 1,3-propanediol, 1,2-propanediol,(s)-(+)-1,2-propanediol, 2-methyl-1,3-propanediol,2,2-dimehyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 22diiethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, (R)-(−)-1,3-butanediol,(S)-(+)-1,3-butanediol, (±)-1,2-butanediol, 2,3-butanediol,meso-2,3-butanediol, (2R,3R)-(−)-2,3-butanediol,(2S,3S)-(+)-2,3-butanediol, 3,3-dimethyl-1,2-butanediol, pinacol,1,5-pentanediol, 1,4-pentanediol, 1,2-pentanediol, 2,4-pentanediol,(2R,4R)-(−)-pentanediol, (2S,4S)-(+)-pentanediol,2-methyl-2,4-pentanediol, (R)-(−)-2-methyl-2,4-pentanediol,2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol,1,6-hexanediol, 1,5-hexanediol, (±)-1,2-hexanediol, 2,5-hexanediol,2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol,1,2-decanediol, 1,12-dodecanediol, (±)-1,2-dodecanediol,cis-1,2-cyclopentanediol, trans-1,2-cyclopentanediol,1,3-cyclopentanediol, trans-1,2-cyclohexanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 2,5-dimethylcyclohexane-1,4-diol,2,5-isopropylcyclohexane-1,4-diol, cis-1,2-cyclohexanedimethanol,1,4-cyclohexanedimethanol, (+)-cis-p-methane-3,8-diol,(−)-trans-p-methane-3,8-diol, (±)-trans-1,2-cycloheptanediol,cis-1,2-cyclooctanediol, trans-1,2-cyclooctanediol, 1,4-cyclooctanediol,cis-1,5-cyclooctanediol,4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]-decane,(1R,2R,3S,5R)-(−)-pinandiol, 1,5-decalindiol,3-cyclohexane-1,1-dimethanol, (±)-trans-2-cyclohexane-1,4-diol,trans-p-ment-6-ene-2,8-diol, cis-3,5-cyclohexadiene,5-norbonene-2,2-dimethanol,(±)-(2-endo,3-exo)-bicyclo[2.2.2]-oct-5-ene-2,3-dimethanol,1,1,1-tris(hydroxymethyl)ethane, (R)-(+)-1,2,4-butanetriol,(S)-(−)-1,2,4-butanetriol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol,(±)-i,2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, ethanolamine,2-hydroxyethylhydrazine, 3-amino-1-propanol, DL-1-amino-2-propanol,4-amino-1-butanol, (±)-2-amino-i -butanol), 5-amino-1-pentanol,DL-2-amino-1-pentanol, 6-amino-1-hexanol, 2-(2-aminoethoxy)ethanol,2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2-(propylamino)ethanol,diethanolamine, diisopropanolamine, 2-(butylamino)ethanol,N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine,triethanolamine, triisopropanolamine,1-[N,N-bis(2-hydroxyethyl)amino]-2-propanol, catechol, 3-methylcatechol,4-methylcatechol, 4-tert-butylcatechol, DL-3,4-dihydroxyphenylglycol,3,5-diisopropylcatechol, 3,5-di-tert-butylcatechol, resorcinol,2-methylresorcinol, 4-ethylresorcinol, 4-hexylresorcinol,4-dodecylresorcinol, 5-pentylresorcinol, 5-pentadecylresorcinol,2,5-dimethylresorcinol, hydroquinone, methyIhydroquinone,tert-butyihydroquinone, 2,3-dimethylhydroquinone,2,5-di-tert-butylhydroquinone,2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, trimethylhydroquinone,1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,bis(2-hydroxyphenyl)methane, (±)-hydrobenzoin, meso-hydrobenzoin,(R,R)-(+)-hydrobenzoin, (S,S)-(−)-hydrobenzoin, benzopinacole,1,4-benzenedimethanol, α,α,α′,α′-tetramethyl-1,4-benzenedirnethanol,1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,2′-biphenyldimethanol,3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol,(±)-1-phenyl-1,2-ethanediol, (S)-(+)-1-phenyl-1,2-ethanediol,(R)-(−)-1-phenyl-1,2-ethanediol, (R)-(+)-1,1,2-triphenyl-1,2-ethanediol,4,4′-biphenol, phenylhydroquinone, bis(4-hydroxyphenyl)methane,4,4′-isopropylidenediphenol, 4,4′-(1,4-diisopropylidenediphenol),2,2-bis(4-hydroxy-3-methylphenyl)propane,1,1,1-tri(4-hydroxyphenyl)ethane, meso-hexestrol, 1,2-ethanedithiol,1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol,1,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol,1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethanol,1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto-1,2-propanediol,2,3-dimercapto-1-propanol, dithiothreitol, dithioerythreitol,2-mercaptoethyl ether, 1,4-dithiane-2,5-diol,2,5-dimethyl-2,5-dihydroxy-1,4-dithiane,1,5,9,13-tetrathiacyclohexadecane-3,11-diol,1,5,9,13,17,21-hexathiacyclotetracosane-3,11,19-triol, ethyleneamine,1,3-diaminopropane, 1,2-diaminopropane, 14-diaminobutane,1,2-diamino-2-methylpropane, 1,6-hexanediamine, 1,7-diaminoheptane,1,8-diaminooctane, 2,5-dimethyl-2,5-hexanediamine, 1,9-diaminononane,1,10-diaminodecane, 1,12-diaminododecane, spermidine, 4,4′-methylenebis(cyclohexylarmine),4,4′-methylenebis(2-methylcyclohexylamine), 1,4-diaminocyclohexane,1,3-cyclohexanebis(methylamine), 1,8-diamino-p-methane,4,4′-trimethylenedipiperidine, 2-piperidinethanol, 3-piperidinethanol,4-hydroxypiperidine, 4,4′-trimethylenebis(1-piperidinethanol),2,2,6,6-tetramethyl-4-piperidinol, piperazine, 2,6-dimnethylpiperazine,1,4-bis(2-hydroxyethyl)piperazine, homopiperazine,1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, cyclene,1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclotetradecane,2-anilinoethanol, N-phenyldiethanolarnine, 3-aaminophenol,3-aminothiophenol, 4,4′-ethylenedianiline, 3,3′-methylenedianiline,4,4′-ethylenedianiline, 4-aminophenyl ether, 4-aminophenol,4-aminophenethyl alcohol, 4,4′-methylenebis(2,6-dimethylaniine),4,4′-methylenebis(2,6-diehtylaniline),4,4′-methylenebis(2,6-diisopropylaniline),3,3′,5,5′-tetramethylbenzidine, 1,4-phenylenediamine,N,N′-diphenyl-1,4-phenylenediamine, 2,7-diaminofluorene,N,N′-dibenzylethylenediamine, (±)-syneprine,4-hydroxy-4-phenylpiperidine, 1,3-bis(phenylphosphino)propane,1,2-bis(phophino)benzene, 4,4′-isopropylidenedicyclohexanol,4,4′-(hexafluoroisopropyllidene)diphenol,4,4′-(phenylenediisopropylidene)bisphenol and 1,2-bis(phosphino)ethane.

The metallocene catalysts are prepared by reacting the metallocenecompounds (A) or (B) with the compounds having at least two functionalgroups (C), (D) or (E) in an organic solvent. The molar ratio oftransition metal of the metallocene compound to the compound having atleast two functional groups is in the range of 1:0.01˜1:000 andpreferably 1.0.1˜1:20. The reaction temperature is in the range of −80°C.˜300° C. and preferably 0° C.˜150° C. The weight ratio of an organicsolvent to the reactants is in the range of 0.1:1˜1000:1 and preferably1:1˜100:1.

The metallocene catalyst according to the present invention is employedwith a co-catalyst in order to prepare polystyrene having a syndiotacticstructure or polyolefin having improved physical properties. Theco-catalyst is an organometallic compound or a mixture ofnon-coordinated Lewis acid and alkylaluminium as is widely known. Theorganometallic compound is an alkylaluminoxane or an organoaluminiumcompound. The representative examples of alkylaluminoxane aremethylaluminoxane (MAO) and modified methylaluminoxane (MMAO).

The organoaluminium compound is aluminoxane having the structural unitrepresented by the general formula (F). There are aluminoxane having achain structure represented by the general formula (G) and aluminoxanehaving cyclic structure represented by the general formula

wherein R′ is an alkyl group of C₁₋₆ and q is an integer of 0 to 100.

The olefin or styrene polymerization employs a new metallocene catalystaccording to the present invention and a co-catalyst such asorganometallic compound. The component ratio of the new metallocenecatalyst to organometallic compound is the same as the molar ratio of atransition metal (IV) in the new metallocene catalyst to the aluminiumin the organometallic compound. That is, the molar ratio of thetransition metal to aluminium is in the range of 1:1 to 1:1×10⁶ andpreferably in the range of 1:10 to 1:1×10⁴.

The co-catalyst used in the present invention is a mixture ofnon-coordinated Lewis acid and alkylaluminium. Examples ofnon-coordinated Lewis acid include N,N-dimethylammoniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, and ferroceriumtetrakis(pentafluorophenyl)borate. Examples of alkylaluminium includetrimethylaluminium, triethylaluminium, diethylaluminium chloride,triisobutylaluminium, diisobutylaluminium chloride, diisobutylalurniniumhydride, tri(n-butyl)aluminium, tri(n-propyl)aluminium, andtriisopropylaluminium.

The molar ratio of non-coordinated Lewis acid to a transition metal inthe catalyst system according to the present invention is preferably inthe range of 0.1:1˜20:1. The molar ratio of a transition metal toalkylaluminium in the catalyst system is preferably in the range of1:1˜1:3000 and more preferably in the range of 1:50˜1:1000.

The reaction temperature for styrene or olefin polymerization by usingthe catalyst system according to the present invention is preferably inthe range of 0˜140° C. and more preferably in the range of 30˜100° C.

The monomers for polymerization by using the catalyst system accordingto the present invention are a styrene, a styrene derivative, or anethylenically unsaturated compound Those monomers can be homopolymerizedor copolymerized.

The styrene and styrene derivative are represented by the generalformulae (I) or (J):

wherein J¹ in the general formula (I) is a hydrogen atom; a halogenatom; or C, O, Si, P, S, Se or Sn, and m is an integer of 1 to 3, J¹ maybe different substituents independently of each other if m is 2 or 3;and J¹ in the general formula (J) is the same as defined in the formula(I), J² is a substituent composed of 2 to 10 carbon atoms having atleast one unsaturated bond, m is an integer of 1 to 3, and n is aninteger of 1 or 2, in which the benzene ring may independently havedifferent substituents if m is over 2 and n is 2.

The illustrative examples of the compounds represented by the generalformula (I) include alkylstyrene, halogenated styrene,halogen-substituted alkylstyrene, alkoxystyrene, vinylbiphenyl,vinylphenylnaphthalene, vinylphenylanthracene, vinyphenylpyrene,trialkylsilybiphenyl, trialkylstannylbiphenyl compound,alkylsilystyrene, carboxymethylstyrene, alkylester styrene,vinylbenzenesulfonic acid ester, and vinylbenzyldialkoxy phosphate.

The alkylstyrene includes styrene, methylstyrene, ethylstyrene,n-butylstyrene, p-methylstyrene, p-tert-butylstyrene, anddimethylstyrene.

The halogenated styrene includes chlorostyrene, bromostyrene, andfluorostyrene.

The halogenated alkylstyrene includes chloromethylstyrene,bromomethylstyrene, and fluoromethylstyrene.

The alkoxystyrene includes methoxystyrene, ethoxystyrene, andbutoxystyrene.

The vinylbiphenyl includes 4-vinylbiphenyl, 3-vinylbiphenyl, and2-vinylbiphenyl.

The vinylphenylnaphthalene includes 1-(4-vinylphenylnaphthalene),2-(4-vinylphenylnaphthalene), 1-(3-vinylphenylnaphthalene),2-(3-vinylphenylnaphthalene), and 1-(2-vinylphenylnaphthalene).

The vinylphenylanthracene includes 1-(4-vinylphenylanthracene,2-(4-vinylphenyl)anthracene, 9-(4-vinylphenyl)anthracene,1-(3-vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene, and1-(2-vinylphenyl)anthracene.

The vinylphenylpyrene includes 1-(4-vinylphenyl)pyrene,2-(4-vinylphenyl)pyrene, 1-(3-vinylphenyl)pyrene,2-(3-vinylphenyl)pyrene, 1-(2-vinylphenyl)pyrene, and2-(2-vinylphenyl)pyrene.

The trialkyksilyvinylbiphenyl includes 4-vinyl-4-trimethylsilybiphenyl.

The trialkylstannylbiphenyl includes 4-vinyl-4-trimethylstannylbiphenyl.

The alkylsilystyrene includes p-trimethylsilystyrene,m-trimethylsilystyrene, o-trimethylsilystyrene, p-triethylsilystyrene,m-triethylsilystyrene, and o-triethylsilystyrene.

The illustrative examples of the compounds represented by the generalformula (J) include divinylbenzene such as p-divinylbenzene andm-divinylbenzene; trivinylbenzene; and aryl styrene such asp-arylstyrene and m-arylstyrene.

Also, the ethylerncally unsaturated monomer is represented by thegeneral formula (K):

wherein E¹, E², E³ and E⁴ are respectively functional groups which areselected the group of a hydrogen atom; a halogen atom; and substituentscontaining at least one atom selected from the group consisting of C, O,Si, P, S, Se and Sn. E¹, E², E³ and E⁴ are respectively able to havefunctional groups which are different from each other.

The illustrative examples of the compounds represented by the formula(K) are α-olefin, cyclic olefin, diene, vinylketone, acrolein,acrylonitrile, acrylamide, acrylic acid, and vinyl acetate. Examples ofα-olefin include ethylene, propylene, 1-butene, 1-hexene, and 1-octene.

Examples of cyclic olefin include cyclobutene, cyclopentene, cylohexene,3-methylcyclopentene, 3-methylcyclohexene, and norbonene.

Examples of diene include 1,3-butadiene, isoprene,1-ethoxy-1,3-butadiene, and chloroprene

Examples of vinylketone include methylvinylketone, phenylvinylketone,ethylvinylketone, and n-propylvinylketone.

Examples of acrolein include acrolein, and metacrolein.

Examples of acrylonitrile include vinylidenecyanide,methoxyacrylonitrile, and phenylacrylonitrile.

Examples of acryloamide include N-methylacryloamide, N-ethylacryloamide,and N-isopropylacryloamide.

Examples of acrylic acid include aryl acrylate, isopropyl acrylate,ethyl acrylate, and acrylic acid chloride.

Examples of vinyl acetate include vinyl acetate and vinyl thioacetate.

A method of polymerization in accordance with the present inventioncomprises contacting monomers selected from the group consisting ofstyrenes, its derivatives, or ethylenically unsaturated compounds withthe catalyst system according to the present invention. Monomers,co-catalyst and metallocene catalyst of this invention may be added in arow to a polymerization reactor. Also, after reacting the metallocenecompound and the compound having at least two functional groups in apolymerization reactor, and co-catalyst and monomers may be added in arow to the polymerization reactor. Further, after reacting themetallocene compound and the compound having at least two functionalgroups in a polymerization reactor being filled with monomers, andco-catalyst may be added to the polymerization reactor. Further, thepolymerization may be performed by reacting the metallocene compound andthe compound having at least two functional groups in a reactor beingfilled with co-catalyst, aging the resultant solution, and adding theaged solution to the polymerization reactor being filled with monomers.The resultant solution is preferably aged at the temperature of 0˜150°C. for 1˜60 min. The copolymerization of monomers selected from thegroup consisting of styrenes, its derivatives, ethylenically unsaturatedcompounds and a mixture thereof may be carried out as in thepolymerization above.

The present invention may be better understood by reference to thefollowing examples which are intended for purposes of illustration andare not to be confined as in any way limiting the scope of the presentinvention, which is defined in the claims appended hereto.

EXAMPLES 1˜18 Synthesis of Catalyst Example 1

Catalyst 1

THF (Tetrahydrofuran) 150 ml was added to a round-bottomed flaskcontaining 126 mmol (4.93 g) of potassium. After the temperature of themixture was decreased to 0° C.,Cp*(1,2,3,4,5-pentamethylcyclopentadiene) of 126 mmol (17.17 g) wasslowly added to the mixture with stirring and then refluxed. Accordingto proceeding the reaction, white solid was started to be produced. Themixture was refluxed for 1 hr more since white solid was produced Afterthe temperature was again decreased to 0° C., chlorotrimethylsilane of130 mmol (14.12 g) was slowly added with a syringe. After the mixturewas stirred for 2 hrs, it was filtered through celite to obtaintransparent yellowish solution THF was evaporated under the vacuum(about 0.1 torr) to give a product which trimethylsilane is bonded toCp*(1,2,3,4,5-pentamethylcyclopentadiene). The yield was 90%.

The product which trimethylsilane was bonded toCp*(1,2,3,4,5-pentamethylcyclopentadiene) was mixed with toluene of 50ml. The mixed solution was dropwisely added to a round-bottomed flaskcontaining TiCl₄ of 88.9 mmol (16.86 g) and toluene of 200 ml withstirring. After the red solution was stirred for 2 hrs, toluene wasevaporated under the vacuum to give a crude solid product. The crudeproduct was washed with n-pentane or n-hexane and dried to obtain theproduct, that is Cp*TiCl which is a metallocene compound. The yield was95%.

Cp*TiCl₃ of 20 mmol (5.79 g) was dissolved in THF (100 ml). To anotherround-bottomed flask containing methanol of 40 mmol (1.28 g), THF (100ml) was added. The reaction temperature was decreased to −78° C. withdryice and acetone. After triethylamine of 41 mmol (4.15 g) wasdropwisely added to the solution with a syringe, the mixture was stirredfor 30 min at −78° C. To the mixed solution, the Cp*TiCl₃/THF solutionwas slowly added at −78° C. with stirring. The temperature was increasedup to room temperature. After the mixture was stirred for 12 hrs, THFwas removed and hexane of 100 ml was added. The solution was stirred for30 min and filtered through celite to give a yellowish solution. Thetemperature of the yellowish solution was decreased under −25° C. toobtain an orange-colored solid. The precipitated orange-colored solidwas separated from hexane and dried under vacuum to give a product ofCp*TiCl(OCH₃)₂ which two chlorides were substituted with two methoxygroups in Cp*TiCl₃. The yield was 75%.

Cp*TiCl(OCH₃)₂ of 10 mmol (2.8 g) is added to a round-bottomed flaskcontaining THF of 100 ml. To another round-bottomed flask containing1,6-hexanediol of 5 mmol (0.591 g), THF (100 ml) was added.

The reaction temperature was decreased to −78° C. with dryice andacetone. After triethylamine of 11 mmol (1.11 g) was dropwisely added tothe solution with a syringe, the mixture was stirred for 30 min at −78°C. To the mixed solution, the Cp*TiCl(OCH₃)₂/TBF solution was slowlyadded at −78° C. with stirring. The temperature was increased to roomtemperature. After the mixture was stirred for 12 hrs, THF was removedand hexane of 100 ml was added. The solution was stirred for 30 min andfiltered through celite to give a yellowish solution. After theyellowish solution was evaporated under vacuum to remove hexane,catalyst 1 was obtained. The yield was 78%.

Example 2

Catalyst 2

Catalyst 2 was prepared in the same method as in Example 1 except forusing 1,10-decanediol instead of 1,6-hexanediol.

Example 3

Catalyst 3

Catalyst 3 was prepared in the same method as in Example 1 except forusing 1,12-dodecanediol instead of 1,6-hexanediol.

Example 4

Catalyst 4

Catalyst 4 was prepared in the same method as in Example 1 except forusing 1,4-cyclohexanediol instead of 1,6-hexanediol.

Example 5

Catalyst 5

Catalyst 5 was prepared in the same method as in Example 1 except forusing 1,4-decalindiol instead of 1,6-hexanediol.

Example 6

Catalyst 6

Catalyst 6 was prepared in the same method as in Example I except forusing 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2.6)]-decane instead of1,6-hexanediol.

Example 7

Catalyst 7

Catalyst 7 was prepared in the same method as in Example 1 except forusing 4,4′-isopropylidenediphenol instead of 1,6-hexanediol.

Example 8

Catalyst 8

Catalyst 8 was prepared in the same method as in Example 1 except forusing 4,4′-(1,4-phenylenediisopropylidene)bisphenol instead of1,6-hexanediol.

Example 9

Catalyst 9

Catalyst 9 was prepared in the same method as in Example 1 except forusing 2,6-dihydroxynaphthalene instead of 1,6-hexanediol.

Example 10

Catalyst 10

Catalyst 10 was prepared in the same method as in Example 1 except forusing 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene instead of1,6-hexanediol.

Example 11

Catalyst 11

Catalyst 11 was prepared in the same method as in Example 1 except forusing di(ethylene glycol) instead of 1,6-hexanediol.

Example 12

Catalyst 12

Catalyst 12 was prepared in the same method as in Example 1 except forusing N-methyldiethanolamine instead of 1,6-hexanediol.

Example 13

Catalyst 13

Catalyst 13 was prepared in the same method as in Example 1 except forusing triisopropanolamine instead of 1,6-hexanediol, and ⅓ equivalent oftriisopropanolamine for 1 equivalent of Cp*Ti(OCH₃)₂Cl.

Example 14

Catalyst 14

Catalyst 14 was prepared in the same method as in Example 1 except forusing 1,1,1-tris(hydroxymethyl)ethane instead of 1,6-hexanediol, and ⅓equivalent of 1,1,1-tri(hydroxymethyl)ethane for 1 equivalent ofCp*Ti(OCH₃)₂Cl.

Example 15

Catalyst 15

Catalyst 15 was prepared in the same method as in Example 1 except forusing tetraol instead of 1,6-hexanediol, and ¼ equivalent of the tetraolcompound for 1 equivalent of Cp*Ti(OCH₃)₂Cl. The tetraol compound wasprepared by reacting tetraphenylolethane glycidyl ether withmethylmagnesium bromide.

Example 16

Catalyst 16

20 mmol (5.79 g) of Cp*TiCl₃ prepared according to the method of Example1 was dissolved in THF of 100 ml. To another round-bottomed flaskcontaining methanol of 20 mmol (0.64 g), THF (100 ml) was added. Thereaction temperature was decreased to −78° C. with dryice and acetone.After triethylamine of 21 mmol (2.08 g) was dropwisely added to thesolution with a syringe, the mixture was stirred for 30 min at −78° C.The resultant solution was slowly added to the Cp*TiCl₃/THF solution at−78° C. with stirring. The temperature was increased up to roomtemperature. After the mixture was stirred for 12 hrs, THF was removedunder vacuum and hexane of 100 ml was added. The solution was stirredfor 30 min and filtered through celite to give an orange-coloredsolution. The temperature of the orange-colored solution was decreasedunder −25° C. to obtain an orange-colored solid. The precipitatedorange-colored solid was separated from n-hexane and dried under vacuumto give a product of Cp*TiCl₂(OCH₃) which one chloride was substitutedto one methoxy group in Cp*TiCl₃. The yield was 70%.

Cp*TiCl₂(OCH₃) of 10 mmol (2.8 g) was added to a round-bottomed flaskcontaining TBF of 100 ml. To another round-bottomed flask containing1,10-decanediol of 10 mmol (1.743 g), THF (100 ml) was added. Thereaction temperature was decreased to −78° C. with dryice and acetone.After triethylamine of 22 mmol (2.22 g) was dropwisely added to thesolution with a syringe, the mixture was stirred for 30 min at −78° C.The Cp*TiCl₂(OCH₃)/THF solution was slowly added to the 1,10-decanedioland triethylamine/TBF solution at −78° C. with stirring. The temperaturewas increased up to room temperature. After the mixture was stirred for12 hrs, the solution was filtered through celite to give a yellowishsolution. After the yellowish solution was evaporated under vacuum toremove THF, the catalyst 16 was obtained. The yield was 65%.

Example 17

Catalyst 17

After Cp*TiCl₃ was prepared in the method as in Example 1, Cp*TiCl₃ of20 mmol (5.79 g) was added to a round-bottomed flask containing tolueneof 100 ml. To another round-bottomed flask containing2,2-Bis(4-hydroxy-3-methylpheyl)propane 30 mmol (7.69 g), toluene (100ml) was added. After triethylamine of 61 mmol (6.17 g) was dropwiselyadded to the solution with a syringe, the mixture was stirred for 10 minat room temperature. The temperature was decreased to −78° C. withdryice and acetone The 2,2-Bis(4-hydroxy-3-methylpheyl)propane andtriethylamine/toluene solution was slowly added to the Cp*TiCl₃/toluenesolution with stirring at −78° C. After the temperature was increased toroom temperature and the mixed solution was stirred for 15 hrs. Themixed solution was filtered through celite to give a yellowish solution.After the yellowish solution was evaporated under vacuum to removetoluene, catalyst 17 was obtained The yield was 85%.

Example 18

Catalyst 18

Catalyst 18 was prepared in the same method as in Example 17 except forusing 4,4′-isopropylidenediphenol instead of2,2-Bis(4-hydroxy-3-methylpheyl)propane.

Example 19

Styrene Polymerization (Solution Polymerization)

The styrene polymerization was performed using the new metahocenecatalysts 1˜18 prepared in Examples 1˜18.

The polymerization reaction was proceeded with a metallocene catalysthaving a concentration (actually, concentration of titanium) of 4×10⁻⁶mol, styrene monomer of 5 cc, toluene of 80 cc, and a modifiedmethylaluminoxane having a concentration of aluminium of 1×10⁻³ mol, for30 min and at 70° C.

It was used a temperature-controlling equipment, a magnetic stirrer or amechanical stirrer for the styrene polymerization. The polymerizationwas performed in a glass reactor with a valve capable of applyingmonomer and nitrogen gas. After purified toluene (80 cc) was added tothe glass flask filled with nitrogen gas instead of air, the purifiedstyrene (5 cc) was again added, and then modified methylaluminoxane(concentration of aluminium=1×10⁻³ mol) as a co-catalyst was added withstirring. To the above mixed solution, a certain amount of a catalyst(concentration of titanium=4×10⁻⁶ mol) was added to start polymerizingof the monomer. After the solution was stirred for a while, a smallamount of methanol was added to stop proceeding polymerization. Theobtained mixture was poured into methanol containing hydrogen chloride(HCl) to give a styrene polymer product. The crude styrene polymerproduct was washed with methanol, filtered, and vacuum-dried to obtain apure styrene polymer. The physical properties of the polystyreneobtained by polymerization were shown in Table 1.

TABLE 1 Activity Stereo- Molecular Molecular Melting Catalyst Yield Kg ·PS/ regularity weight weight point (Example) (g) [Ti][St]hr (%) (× 10³)distribution (° C.) Catalyst 1 1.95 22342 97 232 2.54 271 Catalyst 21.97 22571 98 245 2.31 271 Catalyst 3 1.97 22571 98 240 2.21 271Catalyst 4 1.96 22456 97 210 2.13 270 Catalyst 5 1.93 22113 96 215 2.16270 Catalyst 6 1.94 22227 97 205 2.21 271 Catalyst 7 1.87 21425 98 2342.10 271 Catalyst 8 1.91 21884 98 235 2.01 270 Catalyst 9 1.90 21769 97241 2.05 271 Catalyst 10 1.95 22342 98 243 2.03 270 Catalyst 11 1.3014896 95 156 3.01 270 Catalyst 12 1.42 16269 95 158 3.02 269 Catalyst 131.65 18905 96 210 2.50 270 Catalyst 14 1.60 18332 96 208 2.30 271Catalyst 15 1.35 15467 95 154 3.01 269 Catalyst 16 2.01 23029 97 2462.30 271 Catalyst 17 2.81 32195 99 285 1.98 271 Catalyst 18 3.02 3460199 231 2.01 271

Example 20

Styrene Polysezation (Bulk Polymerization)

The styrene polymerization was performed using several catalystsselected from the group of the new metallocene catalysts 1˜18 preparedin, Examples 1˜18.

The polymerization reaction was proceeded with a catalyst having aconcentration (actually, concentration of titanium) of 1.5×10⁻⁵ mol,styrene monomer of 200 cc, trijsobutylamine having a concentration of1.2×10⁻² mol, and modified methylaluminoxane having a concentration ofaluminium of 1.5×10⁻³ mol, for 1 hour and at 70° C.

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified styrene (200 cc) wasadded to a glass flask filled with nitrogen gas instead of air, and thentriisobutylaluminium (1.2×10⁻² mol) were added. To the resultantsolution, modified methylaluminoxane (concentration ofaluminium=1.5×10⁻³ mol) as a co-catalyst wa s added with stirring. Tothe above mixed solution, a certain amount of a catalyst (concentrationof titanium=1.5×10⁻⁵ mol) was added to start polymerizing of themonomer. After the solution was stirred for a while, a small amount ofmethanol was added to stop proceeding polymerization. The obtainedmixture was poured into methanol containing hydrogen chloride (HCl) t ogive a styrene polymer product.

The crude styrene polymer product was washed with methanol, filtered,and vacuum-dried to obtain a pure styrene polymer. The physicalproperties of the polystyrene obtained by polymerization are shown inTable 2.

TABLE 2 Activity Stereo- Molecular Molecular Melting Catalyst Yield Kg ·PS/ regularity weight weight point (Example) (g) [Ti][St]hr (%) (× 10³)distribution (° C.) Catalyst 2 110 4200 95 430 2.34 271 Catalyst 4 1124276 95 421 2.31 271 Catalyst 9 115 4391 96 405 2.21 271 Catalyst 16 1284887 97 540 2.13 272 Catalyst 18 138 5269 99 534 2.21 273

Example 21

Preparation of Catalyst and the Solution Polymerization of Styrene inOne Reaction Container

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. The purified toluene (40 cc) wasadded to a glass flask filled with nitrogen gas instead of air.Pentamethylcyclopentadienyltitaniumtruchloride [Cp*TiCl₃] of 4×10⁻⁶ mol(1.16 mg) diluted with toluene (20 ml) was added. To the above mixture,the solution composed of 4,4-isopropylidenediphenol of 6×10⁻⁶ mol (1.37mg) and triethylamine of 12.05×10⁻⁶ mol (1.22 mg) in toluene of 20 mlwas added with stirring. After the mixed solution was stirred for 1 hourat 100° C. the reaction temperature was decreased to 70° C.Methylaluminoxane (concentration of aluminium=1.0×10⁻³ mol) as aco-catalyst was added to the resultant solution with stirring. Thepurified styrene (5 cc) was added to the solution to start polymerizingand stirred for 30 min. A small amount of methanol was added to thesolution to stop polymerizing.

The obtained mixture was poured into methanol containing hydrogenchloride (HCl) to give a styrene polymer product. The crude styrenepolymer product was washed with methanol, filtered, and vacuum-dried toobtain a pure styrene polymer The physical properties of the polystyreneobtained by polymerization are shown in Table 3.

TABLE 3 Activity Stereo- Melting Catalyst Yield KG · PS/ regularitypoint (Example) (g) [Ti][St]hr (%) (°C.) Catalyst 21 2.78 31852 96 271

Example 22

Preparation of Catalyst and the Bulk Polymerization of Styrene in OneReaction Container

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified styrene (150 cc) wasadded to a glass flask filled with nitrogen gas instead of air,pentamethylcyclopentadienyltitanium trichloride [Cp*TiCl₃] of 1.5×10⁻⁵mol (4.34 mg) diluted with the purified styrene (20 cc) was added. Tothe above mixture, the solution composed of 4,4′-isopropylidenediphenolof 2.25×10⁻⁵ mol (5.14 mg) and triethylamine of 4.52×10⁻⁵ mol (4.57 mg)in the purified styrene of 30 cc was added with stirring. After themixed solution was stirred for 5 hours at room temperature, the reactiontemperature was raised up to 70° C. Triisobutylaluminium (1.2×10⁻² mol)and methylaluminoxane (concentration of aluminium 1.5×10⁻³ mol) as aco-catalyst were added to the resultant solution with stirring to startpolymerizing and stirred for 1 hour. A small amount of methanol wasadded to the solution to stop polymerizing. The obtained mixture waspoured into methanol containing hydrogen chloride (HCl) to give astyrene polymer product The crude styrene polymer product was washedwith methanol, filtered, and vacuum-dried to obtain a pure styrenepolymer. The physical properties of the polystyrene obtained bypolymerization are shown in Table 4.

TABLE 4 Activity Catalyst Yield Kg · PS/ Stereoregularity (Example) (g)[Ti][St]hr (%) Catalyst 22 135 5155 99

Example

Modified Method for Solution Polymerization of Styrene (I)

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. Purified toluene (40 cc) was added toa glass flask filled with nitrogen gas instead of the air.Pentamethylcyclopentadienyltitanium trichloride [Cp*TiCl₃],pentamethylcyclopentadienylmethoxytitanium dichloride [Cp*Ti(OMe)Cl₂],or pentamethylcyclopentadienyldimethoxytitanium chloride [Cp*Ti(OMe)₂Cl]of 4×10⁻⁶ mol diluted with toluene (20 cc) was added to the flaskcontaining the purified toluene of 40 cc. To the above solution, thesolution composed of triethylamine and the compound having at least twofunctional groups which is represented in the following Table 5 intoluene of 20 cc were added with stirring After the mixed solution wasstirred for 5 hours at room temperature, the reaction temperature wasraised up to 70° C. Methylaluminoxane (concentration of aluminium=1×10⁻³mol) as a co-catalyst was added to the resultant solution with stirring.Purified styrene (5 cc) was added to the solution to start polymerizingand stirred for 30 min. A small amount of methanol was added to thesolution to stop polymerizing.

The obtained mixture was poured into methanol containing hydrogenchloride (HCl) to give a styrene polymer product. The crude styrenepolymer product was washed with methanol, filtered, and vacuum-dried toobtain a pure styrene polymer. The physical properties of thepolystyrene obtained by polymerization are shown in Table 5.

TABLE 5 Compound Half having metallocene at least two Activity Stereo-catalyst functional groups Mole of Yield Kg · PS/ regularity (mol) (mol)N(C₂H₅)₃ (g) [Ti][St]hr (%) Cp*Ti(OMe)₂Cl 1,10-Decandiol  4 × 10⁻⁶ mol1.71 19610 97 (4 × 10⁻⁶ mol) (2 × 10⁻⁶ mol) Cp*Ti(OMe)Cl₂ 1,10-Decandiol 8 × 10⁻⁶ mol 1.76 20183 97 (4 × 10⁻⁶ mol) (4 × 10⁻⁶ mol) Cp*TiCl₃1,10-Decandiol 12 × 10⁻⁶ mol 2.10 24083 98 (4 × 10⁻⁶ mol) (6 × 10⁻⁶ mol)4,4‘- Cp*TiCl₃ 4,4‘-Isopropylidene- (4 × 10⁻⁶ mol) diphenol 12 × 10⁻⁶mol 2.52 28899 98 (6 × 10⁻⁶ mol)

Example 24

Modified Method for Solution Polymerization of Styrene (II)

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified toluene (40 cc) wasadded to a glass flask filled with nitrogen gas instead of air, purifiedstyrene (5 cc) was added. Pentamethylcyclopentadienyltitaniumtrichloride [Cp*TiCl₃] pentarnethylcyclopentadienylmethoxytitaniumdichloride [Cp*Ti(OMe)Cl₂] orpentamethylcyclopentadienydimethoxyltitanium chloride [Cp*Ti(OMe)₂Cl] of4×10⁻⁶ mol diluted with toluene (20 cc) was added. To the above mixture,the solution composed of triethylamine and the compound having at leasttwo functional groups which is represented in the following Table 6 intoluene of 20 cc were added with stirring. After the mixed solution wasstirred for 5 hours at room temperature, the reaction temperature wasraised up to 70° C. Methylaluminoxane (concentration ofaluminium=1.0×10⁻³ mol) as a co-catalyst was added to the resultantsolution with stirring. After stirred for 30 min, a small amount ofmethanol was added to the solution to stop polymerizing The obtainedmixture was poured into methanol containing hydrogen chloride (HCl) togive a styrene polymer product. The crude styrene polymer product waswashed with methanol, filtered, and vacuum-dried to obtain a purestyrene polymer. The physical properties of the polystyrene obtained bypolymerization are shown in Table 6.

TABLE 6 Compound Half having metallocene at least two Activity Stereo-catalyst functional groups Mole of Yield Kg · PS/ regularity (mol) (mol)N(C₂H₅)₃ (g) [Ti][St]hr (%) Cp*Ti(OMe)₂Cl 1,10-Decandiol  4 × 10⁻⁶ mol1.65 19610 97 (4 × 10⁻⁶ mol) (2 × 10⁻⁶ mol) Cp*Ti(OMe)Cl₂ 1,10-Decandiol 8 × 10⁻⁶ mol 1.71 19610 97 (4 × 10⁻⁶ mol) (4 × 10⁻⁶ mol) Cp*TiCl₃1,10-Decandiol 12 × 10⁻⁶ mol 2.01 23050 98 (4 × 10⁻⁶ mol) (6 × 10⁻⁶ mol)Cp*TiCl₃ 4,4‘-Isopropylidene- (4 × 10⁻⁶ mol) diphenol 12 × 10⁻⁶ mol 2.3426835 98 (6 × 10⁻⁶ mol)

Example 25

Modified Method for Solution Polymerization of Styrene (III)

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified toluene (40 cc) wasadded to a reaction container 1 filled with nitrogen gas instead of air,purified styrene was added. To another reaction container 2,pentamethylcyclopentadienyltitanium trichloride [Cp*TiCl₃] andpentamethylcyclopentadienyldimethoxytitanium monochloride[Cp*Ti(OMe)₂Cl] of 4×10⁻⁶ mol diluted with toluene (20 cc) were added.To the mixed solution in reaction container 2, the solution composed oftriethylamine and the compound having at least two functional groupswhich is represented in the following Table 7 in toluene of 20 cc wasadded with stirring. After the mixed solution was stirred for 5 hours atroom temperature, the reaction temperature was raised up to 70° C.Methylalurrinoxane (concentration of aluminium=1.0×10⁻³ mol) as aco-catalyst was added to the resultant solution with stirring and agedfor 10 min. The aged mixed solution in reaction container 2 was added tothe reaction container 1. The obtained mixture was poured into methanolcontaining hydrogen chloride (HCl) to give a styrene polymer product.The crude styrene polymer product was washed with methanol, filtered,and vacuum-dried to obtain a pure styrene polymer. The physicalproperties of the polystyrene obtained by polymerization are shown inTable 7.

TABLE 7 Compound Half having metallocene at least two Activity Stereo-catalyst functional groups Mole of Yield Kg · PS/ regularity (mol) (mol)N(C₂H₅)₃ (g) [Ti][St]hr (%) Cp*Ti(OMe)₂Cl 1,10-Decandiol  4 × 10⁻⁶ mol1.76 20183 98 (4 × 10⁻⁶ mol) (2 × 10⁻⁶ mol) 4,4‘- Cp*TiCl₃4,4‘-Isopropylidene- 12 × 10⁻⁶ mol 2.36 27064 98 (4 × 10⁻⁶ mol) diphenol(6 × 10⁻⁶ mol)

Example 26

Stability Test of the Catalyst for the Air and Moisture

The catalysts 2, 16 and 18 prepared in the same manner as in Examples 2,16 and 18 were exposed to air for one day. The styrene polymerizationwas performed in the same manner as in Example 19 with the air-exposedcatalysts The styrene polymerization was performed in the same manner asin Example 19 with the catalyst which was not exposed to the air andmoisture. The physical properties of the polystyrenes are shown in Table8.

TABLE 8 Activity Stereo- Kg · PS/ regularity Catalyst Yield(g)[Ti][St]hr (%) Catalyst 2: 0.89 21654 97 no exposure to the air Catalyst2: 1.98 11228 95 exposure to the air Catalyst 16: 2.31 26467 98 noexposure to the air Catalyst 16: 1.61 18446 96 exposure to the airCatalyst 18: 2.81 32195 98 no exposure to the air Catalyst 18: 1.9322113 96 exposure to the air

Example 27

Copolymerization of Styrene with P-methylstyrene

The polymerization reaction was proceeded with concentration of thecatalyst 2, 16 or 18 (concentration of titanium of 4×10⁻⁶ mol), styrenemonomer of 5.44 cc, p-methylstyrene of 0.325 cc, toluene of 8 cc andconcentration of aluininum contained in modified methylaluminoxane1×10⁻³ mol, for 30 min and at 70° C.

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified toluene (80 cc) wasadded to a glass flask filled with nitrogen gas instead of air, purifiedstyrene (5.44 cc) and p-methylstyrene (0.325 cc) was added, and thenmodified methylaluminoxane (concentration of aluminium=1×10⁻³ mol) as aco-catalyst was added with stirring. To the above mixed solution, acertain amount of a catalyst (concentration of titanium=4×10⁻⁶ mol) wasadded to start polymerizing of the monomer. After the solution wasstirred for a while, a small amount of methanol was added to stopproceeding polymerization. The obtained mixture was poured into methanolcontaining hydrogen chloride (HCl) to give a styrene polymer product.The crude styrene polymer product was washed with methanol, filtered,and vacuum-dried to obtain a pure styrene polymer. The physicalproperties of the copolymerized styrene obtained by polymerization areshown in Table 9.

TABLE 9 Activity Stereo Content of Catalyst Yield Kg · PS/ regularitymonomer Tg Tm (Example) (g) [Ti][St]hr (%) (%) (° C.) (° C.) Catalyst 22.32 23200 99 7.1 100 245 Catalyst 16 2.81 28100 99 7.5 101 245 Catalyst18 3.24 32400 99 8.1  99 243

Example 28

Copolymerization of Styrene with Divinylbenzene

The polymerization reaction was proceeded with concentration of thecatalyst 2, 16 or 18 (concentration of titanium of 4×10⁻⁶ mol), styrenemonomer of 5 cc, divinylbenzene of 0.082 cc, toluene of 80 cc, and themodified methylaluminoxane having concentration of aluminium of ×10⁻³mol, for 30 min and at 70° C.

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. After purified toluene (80 cc) wasadded to a glass flask filled with nitrogen gas instead of air, purifiedstyrene (5 cc) and divinylbenzene (0.082 cc) was added, and thenmodified methylaluminoxane (concentration of aluminium=1×10⁻³ mol) as aco-catalyst was added with stirring. To the above mixed solution, acertain amount of a catalyst (concentration of titanium=4×10⁻⁶ mol) wasadded to start polymerizing of the monomer. After the solution wasstirred for a while, a small amount of methanol was added to stopproceeding polymerization. The obtained mixture was poured into methanolcontaining hydrogen chloride (HCl) to give a styrene polymer product.The crude styrene polymer product was washed with methanol, filtered,and vacuum-dried to obtain a pure styrene polymer. The physicalproperties of the copolymerized styrene obtained by polymerization areshown in Table 10.

TABLE 10 Activity Stereo- Content of Catalyst Yield Kg · PS/ regularitymonomer Tg Tm (Example) (g) [Ti][St]hr (%) (%) (° C.) (° C.) Catalyst 21.64 18788 99 0.9 100 254 Catalyst 16 1.76 20163 99 0.9  99 255 Catalyst18 2.02 23142 99 0.9  99 253

Example 29

Copolymerization of Styrene with 1,3-Butadiene

The polymerization reaction was proceeded with concentration of thecatalyst 2, 16 or 18 (concentration of titanium of 4×10⁻⁶ mol), styrenemonomer of 0.3 mol, 1,3-butadiene of 0.30 mol, and the modifiedmethylaluminoxane having concentration of aluminium of 1×10⁻² mol, for 4hrs and at 30° C.

A temperature-controlling equipment and a magnetic stirrer or amechanical stirrer were used for the styrene polymerization. Thepolymerization was performed in a glass reactor with a valve capable ofapplying monomer and nitrogen gas. The purified styrene (0.3 mol) and1,3-butadiene (0.3 mol) was added to a glass flask filled with nitrogengas instead of air, and then modified methylaluminoxane (concentrationof aluminium=1×10⁻² mol) as a co-catalyst was added with stirring. Tothe above mixed solution, a certain amount of a catalyst (concentrationof titanium=4×10⁻⁶ mol) was added to start polymerizing of the monomer.After the solution was stirred for 4 hours, a small amount of methanolwas added to stop proceeding polymerization. The obtained mixture waspoured into methanol containing hydrogen chloride (HCl) to give astyrene polymer product. The crude styrene polymer product was washedwith methanol, filtered, and vacuum-dried to obtain a pure styrenepolymer. The physical properties of the copolymerized styrene obtainedby polymerization are shown in Table 11.

TABLE 11 Activity Stero- Content of Catalyst Yield Kg · PS/ regularitymonomer Tg Tm (Example) (g) [Ti][St]hr (%) (%) (° C.) (° C.) Catalyst 210.89 113.4 96 8.4 84 267 Catalyst 16 12.73 132.6 95 8.1 86 268 Catalyst18 13.64 142.1 96 8.6 84 269

The stereoregularity in Table 1˜11 was obtained in percent (%) bymeasuring the weight of the polymer which was extracted with methylethyl ketone, corresponding to syndiotactic index (S.I.). Also, thesyndiotacticity of styrene polymer was measured with racemic pentad byusing ¹³C-NMR. The glass transition temperature (Tg) and the meltingpoint (Tm) in Table 1˜11 were measured with Differential ScanningCalorimetry (DSC), by heating up to 300° C., resting for 5 min, cooling,and heating the test sample The rate of temperature elevation was 10°C./min.

What is claimed is:
 1. A metallocene catalyst for olefin or styrenepolymerization prepared by reacting a metallocene compound representedby the general formulae: MR¹ _(a)R² _(b)R³ _(c)R⁴ _(4−(a+b+c))  (A) orMR¹ _(d)R² _(e)R³ _(3−(d+e))  (B) and a compound having at least twofunctional groups represented by the general formulae (C), (D), or (E):T²—YR⁵Y′—T¹  (C)

wherein M in the formulae (A) and (B) represents a transition metal ofGroup IV, V or VI of the Periodic Table of Elements; R¹, R², R³, and R⁴are selected from the group consisting of a hydrogen atom; a halogenatom; an alkyl group, a cycloalkyl group, and an alkoxy group of C₁₋₂₀;an aryl group, an alkylaryl group, and an arylalkyl group of C₆₋₂₀, asubstituted or unsubstituted cyclopentadienyl group and derivativesthereof, a substituted or unsubstituted indenyl group and derivativesthereof, a substituted or unsubstituted fluorenyl group and derivativesthereof, wherein at least one of R¹, R², R³, and R⁴ is a substituted orunsubstituted cyclopentadienyl group and derivatives thereof, asubstituted or unsubstituted indenyl group and derivatives thereof, asubstituted or unsubstituted fluorenyl group and derivatives thereof; a,b and c are integers from 0 to 4; d and e are integers from 0 to 3;wherein T¹, T², T³ and T⁴ in the formulae (C), (D), and (E) are selectedfrom the group consisting of a hydrogen atom; an alkyl group, acycloalkyl group and an alkoxy group of C₁₋₂₀; an aryl group, analkylaryl group, and an arylkyl group of C₆₋₂₀; and an alkali metal; Y,Y′, Y″ and Y′″ are selected from the group consisting of O, S, —Nr¹⁷, or—Pr¹⁸, wherein r¹⁷ and r¹⁸ are selected from the group consisting of ahydrogen atom; an alkyl group, a cycloalkyl group and an alkoxy group;an aryl group of, an alkylaryl group, and an arylalkyl group of C₆₋₂₀;R⁵, R⁶, R⁷ and R⁸ are selected from the group consisting of R′, R′—m—R″,and

wherein R′, R″, R′″, and R″″ are selected from the group consisting of alinear alkyl group and a branched alkyl group of C₆₋₂₀; a cycloalkylgroup and a substituted cycloalkyl group of C₃₋₂₀; an aryl group; analkylaryl group and an arylalkyl group of C₆₋₄₀; and r¹⁹ is a hydrogenatom; an alkyl group; a cycloalkyl group and an alkoxy group ofC_(1˜10); and an aryl group, an alkylaryl group and an arylalkyl groupof C₆₋₂₀; and m is selected from the group consisting of an oxygen atom,a sulfur atom, —Nr¹⁷ or —Pr¹⁸, and Sir¹⁷r¹⁸, wherein r¹⁷ and r¹⁸ areselected from the group consisting of a hydrogen atom; an alkyl group, acycloalkyl group and an alkoxy group of C₁₋₁₀; Q is N or —Cr²⁰ whereinr²⁰ is selected from the group consisting of an alkyl group, acycloalkyl group, and an alkon group of C_(1˜10); and an aryl group, analkylaryl group and an arylalkyl group of C_(6˜20); and Z is C, Si, Geor


2. The catalyst for olefin and styrene polymerization of claim 1 whereinsaid metallocene compound is selected from the group consisting ofpentamethylcyclopentadienyl titanium trichloride,pentamethylcyclopentadienylmethoxy titanium dichloride,pentamethylcyclopentadienyldimethoxy titanium monochloride,1,2,3,4-tetramethylcyclopentadienyl titanium trichloride,1,2,4-trimethylcyclopentadienyl titanium trichloride,1,2-dimethylcyclopentadienyl titanium trichloride,methylcyclopentadienyl titanium trichloride, cyclopentadienyl titaniumtrichloride, pentamethylcyclopentadienylmethyl titanium dichloride, andpentamethylcyclopentadienyldimethyl titanium monochloride.
 3. Thecatalyst for olefin and styrene polymerization of claim 1 wherein saidcompound having at least two functional groups is selected from thegroup consisting of 1,6-hexanediol, 1,12-dodecanediol,1,4-cyclohexanediol, 1,5-decalinediol, 1,1,1-tris(hydroxymethyl)ethane,triisopropanolamine, hydroquinone, 2,6-dihydroxynaphthalene,α,α,α′,α′-tetramethyl-1,4-benzenedimethanol,1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene,4,4′-isopropylidenediphenol, 2,2-bis(4-hydroxy-3-methylphenyl)propane,meso-hexestrol, 1,6-hexanedithiol, 4,4′-isopropylidenedicyclohexanol,4,4′-(hexafluoroisopropylidene)diphenol and4,4′-(1,4-phenylenediisoprorylidene)bisphenol.
 4. The catalyst forolefin and styrene polymerization of claim 1, which is represented bythe general formula (I):

wherein M and M′ are transition metals of Group IV, V, and VI of thePeriodic Table; Cp and Cp′ are selected from the group consisting of acyclopentadienyl group, an indenyl group, a fluorenyl group and aderivative of each group which forms η⁵-bond with a transition metalsuch as M and M′, and Cp and Cp′ are represented by general formulas(a), (b), (c) and (d);

wherein r₁, r², r³, r⁴, r⁵, r⁶, r⁷, r⁸, r⁹, r¹⁰, r¹¹, r¹², r¹³, r¹⁴, r¹⁵and r¹⁶ are selected from the group consisting of a hydrogen atom; analkyl group, a cycloalkyl group and an alkoxy group of C_(1˜20); and anaryl group, an alkylaryl group and an arylalkyl group of C_(1˜20); and fis an integer of 4 to 8; X¹, X², X³ and X⁴ are selected from the groupconsisting of a hydrogen atom; a hydroxy group; a halogen atom; an alkylgroup, a cycloalkyl group and an alkoxy group of C_(1˜20); and an arylgroup, an alkylaryl group and an arylalkyl group of C_(6˜40); and G is agroup connecting between two transition metals and is represented as—YR⁵Y′— and T²—YR⁵Y′—T¹, wherein T¹ and T² are selected from the groupconsisting of an alkyl group, a cycloalkyl group and an alkoxy group ofC₁₋₂₀; and an aryl group, an alkylaryl group and an arylalkyl group ofC₆₋₂₀; Y and Y′ are selected from the group consisting of O, S, —Nr¹⁷and —Pr¹⁸, wherein r¹⁷ and r¹⁸ are selected from the group consisting ofa hydrogen atom; an alkyl group, a cycloalkyl group and an alkoxy groupof C₁₋₁₀; and an aryl group, an alkylaryl group and an arylalkyl groupof C₆₋₂₀); and R⁵ is R′, R′—m—R″ and

wherein R′, R″, R″′ and R″″ are selected from the group consisting of alinear alkyl group and a branched alkyl group of C₆₋₂₀; a cycloalkylgroup and a substituted cycloalkyl group of C₃₋₂₀; and an aryl group, analkylaryl group and an arylalkyl group of C₆₋₄₀; and m is selected fromthe group consisting of an oxygen atom, a sulfur atom, —Nr¹⁷, —Pr¹⁸ andSir¹⁷r¹⁸, wherein r¹⁷ and r¹⁸ are selected from the group consisting ofa hydrogen atom; an alkyl group, a cycloalkyl group and an alkoxy groupof C₁₋₁₀; and an aryl group, an alkylaryl group and an arylalkyl groupof C_(6˜20).
 5. The catalyst for olefin and styrene polymerization ofclaim 1, which is represented by the general formula (II):

wherein M and M′ are transition metals of Groups IV, V, and VI of thePeriodic Table; X¹ and X⁴ are independently selected from the groupconsisting of hydrogen, hydroxy, halogen, C₁₋₂₀ alkyl, C₁₋₂₀ cycloalkyl,C₁₋₂₀ alkoxy, C₆₋₄₀ aryl, C₆₋₄₀ alkylaryl, and C₆₋₄₀ arylalkyl; and Cpand Cp′ are independently selected from the group consisting of asubstituted or unsubstituted cyclopentadienyl group and derivativesthereof, a substituted or unsubstituted indenyl group and derivativesthereof, and a substituted or unsubstituted fluorenyl group andderivatives thereof; G and G′ are —YR⁵Y′— or T²—YR⁵Y′—T¹, wherein T¹ andT² are independently selected from the group consisting of C₁₋₂₀ alkyl,C₁₋₂₀ cycloalkyl, C₁₋₂₀ alkoxy, C₆₋₂₀ aryl, C₆₋₂₀ alkylaryl, and C₆₋₂₀arylalkyl; Y and Y′ are independently selected from the group consistingof O, S, —Nr¹⁷ and —Pr¹⁸, wherein r¹⁷ and r¹⁸ are selected from thegroup consisting of hydrogen, C₁ to C₁₀ alkyl, C₁ to C₁₀ cycloalkyl, C₁to C₁₀ alkoxy, C₆ to C₂₀ aryl, C₆ to C₂₀ alkylaryl, and C₆ to C₂₀arylalkyl; and R⁵ is R′, R′—m—R″ or R′″—N—R″″, wherein R′, R″, R′″ andR″″ are independently selected from the group consisting of C₆ to C₂₀alkyl, C₃ to C₂₀ cycloalkyl, substituted C₃ to C₂₀ cycloalkyl, C₆ to C₄₀aryl, C₆ to C₄₀ alkylaryl, C₆ to C₄₀ arylalkyl; and m is selected fromthe group consisting of oxygen, sulfur, —Nr¹⁷, —Pr¹⁸ and Sir¹⁷r¹⁸. 6.The catalyst for olefin and styrene polymerization of claim 1, which isrepresented by the general formula (III):

wherein M and M′ are transition metals independently selected fromGroups IV, V, and VI of the Periodic Table; Cp and Cp′ are selected fromthe group consisting of substituted and unsubstituted cyclopentadienoland derivatives thereof, substituted and unsubstituted indenyl andderivatives thereof, and substituted and unsubstituted fluorenyl andderivatives thereof; G, G′ and G″ are independently —YR⁵Y′— orT²—YR⁵Y′—T¹, wherein T¹ and T² are independently selected from the groupconsisting of C₁ to C₂₀ alkyl, C₁ to C₂₀ cycloalkyl, C₁ to C₂₀ alkoxy,C₆ to C₂₀ aryl, C₆ to C₂₀ alkylaryl, and C₆ to C₂₀ arylalkyl; Y and Y′are independently selected from the group consisting of O, S, —Nr¹⁷ and—Pr¹⁸, wherein r¹⁷ and r¹⁸ are selected from the group consisting ofhydrogen, C₁ to C₁₀ alyl, C₁ to C₁₀ cycloalkyl, C₁ to C₁₀ alkoxy, C₆ toC₂₀ aryl, C₆ to C₂₀ alkylaryl, and C₆ to C₂₀ arylalkyl; and R⁵ is R′,R′—m—R″ or R′″—N—R″″, wherein R′, R″, R′″ and R″″ are independentlyselected from the group consisting of C₆ to C₂₀ alkyl, C₃ to C₂₀cycloalkyl, C₃ to C₂₀ cycloalkyl, C₆ to C₄₀ aryl, C₆ to C₄₀ alkylaryl,C₆ to C₄₀ arylalkyl; and m is selected from the group consisting ofoxygen, sulfur, —Nr¹⁷, —Pr¹⁸ and Sir¹⁷r¹⁸.
 7. The catalyst for olefinand styrene polymerization of claim 1, which is represented by thegeneral formula (IV):

wherein M, M′ and M″ are transition metals selected from Group IV, V,and VI of the Periodic Table; Cp, Cp′, and Cp″ are independentlyselected from the group consisting of substituted and unsubstitutedcyclopentadienyl and derivatives thereof, substituted and unsubstitutedindenyl and derivatives thereof, and substituted and unsubstitutedfluorenyl and derivatives thereof; X⁵, X⁶, X⁷, X⁸, X⁹, and X¹⁰ areindependently selected from the group consisting of hydrogen, hydroxy,halogen, C₁ to C₂₀ alkyl, C₁ to C₂₀ cycloalkyl, C₁ to C₂₀ alkoxy, C₆ toC₄₀ aryl, C₆ to C₄₀ alkylaryl, and C₆ to C₄₀ arylalkyl; R⁶, R⁷, and R⁹are selected from the group consisting of C₁ to C₁₀ alkyl, C₃ to C₁₀cycloalkyl, C₆ to C₂₀ aryl, C₆ to C₂₀ alkylaryl, and C₆ to C₂₀ arylalkylQ is N or —Cr²⁰; Y and Y′ are independently selected from the groupconsisting of O, S, —Nr¹⁷ and —Pr¹⁸, wherein r¹⁷, r¹⁸, and r²⁰ areselected from the group consisting of hydrogen, C₁ to C₁₀ alkyl , C₁ toC₁₀ cycloalkyl, C₁ to C₁₀ alkoxy, C₆ to C₂₀ aryl, C₆ to C₂₀ alkylaryl,and C₆ to C₂₀ arylalkyl.
 8. The catalyst for olefin and styrenepolymerization of claim 1 which is represented by the general formula(V):

wherein M, M′, M″, and M″′ are independently selected from thetransition metals of Group IV, V, and VI of the Periodic Table; Cp, Cp′,Cp″, Cp″′ are independently selected from the group consisting ofsubstituted and unsubstituted cyclopentadienyl and derivatives thereof,substituted and unsubstituted indenyl and derivatives thereof, andsubstituted and unsubstituted fluorenyl, and derivatives thereof; X⁵,X⁶, X⁷, X⁸, X⁹, X¹⁰, X¹¹, and X¹² are independently selected from thegroup consisting of hydrogen, hydroxy, halogen, C₁ to C₂₀ alkyl, C₁ toC₂₀ cycloalkyl, C₁ to C₂₀ alkoxyl, C₆ to C₄₀ aryl, C₆ to C₄₀ alkylaryl,and C₆ to C₄₀ arylalkyl; R⁶, R⁷, R⁸ and R⁹ are selected from the groupconsisting of C₁ to C₁₀ alkyl, C₃ to C₁₀ cycloalkyl , C₆ to C₂₀ aryl, C₆to C₂₀ alkylaryl, and C₆ to C₂₀ arylalkyl; Y, Y′, Y″, and Y″′ areindependently selected from the group consisting of O, S, —Nr¹⁷ and—Pr¹⁸ wherein r¹⁷ and r¹⁸ are independently selected from the groupconsisting of hydrogen, C₁ to C₁₀ alkyl C₁ to C₁₀ cycloalkyl, C₁ to C₁₀alkoxy, C₆ to C₂₀ aryl, C₆ to C₂₀ alkylaryl, and C₆₋₂₀ arylalkyl; and Zis selected from the group consisting of C, Si, Ge and


9. The metallocene catalyst for olefin and styrene polymerization ofclaim 1 wherein the molar ratio of said metallocene compound to saidcompound having at least two functional groups is from about 1:0.2 toabout 1:100.
 10. The catalyst for styrene and olefin polymerization ofclaim 9 wherein said molar ratio of said metallocene compound to saidcompound having least two functional groups is from about 1:0.25 toabout 1:5.
 11. A catalyst system for styrene and olefin polymerizationcomprising a catalyst according to claim 1 and a co-catalyst.
 12. Thecatalyst system of claim 11 wherein said co-catalyst is anorganometallic compound.
 13. The catalyst system of claim 12 whereinsaid organometallic compound is selected from the group consisting of analkylaluminoxane and an organoaluminium compound.
 14. The catalystsystem of claim 13 wherein said alkylaluminoxane is methylaluminoxane ormodified methylaluminoxane.
 15. The catalyst system of claim 14 whereinsaid organoaluminoxane compound has the structural unit represented bythe general formula (F), and has a chain and a cyclic structurerepresented by the general formulas (G) and (H):

wherein R′ is selected from the group consisting of a hydrogen atom; alinear alkyl group and branched alkyl group of C_(1˜10); a cycloalkylgroup and a substituted cycloalkyl group of C_(3˜20); and an aryl group,an alkylaryl group and an arylalkyl group of C_(6˜20); and q is aninteger.
 16. The catalyst system of claim 12 wherein the molar ratio oftransition metal of said metallocene compound to aluminium of saidorganomettalic compound is from about 1:1 to about 1:10000.
 17. Thecatalyst system of claim 16 wherein said molar ratio is from about 1:10to about 1:3000.
 18. The catalyst system of claim 11 wherein saidco-catalyst is a mixture of a non-coordinated Lewis acid andalkylaluminium.
 19. The catalyst system of claim 18 wherein saidnon-coordinated Lewis acid is selected from the group consisting ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, and ferroceriumtetrakis(pentafluorophenyl)borate.
 20. The catalyst system of claim 18wherein the molar ratio of transition metal of said catalyst to saidnon-coordinated Lewis acid is from about 1:0.1 to about 1:20.
 21. Thecatalyst system of claim 18 wherein said alkylaluminium is selected fromthe group consisting of trimethylaluminium, triethylaluminium,diethylaluminium chloride, triisobutylaluminium, diisobutylaluminiumchloride, diisobutylaluminium hydride, tri(n-butyl)aluminium,tri(n-propyl)aluminium, and triisopropylaluminium.
 22. The catalystsystem of claim 21 wherein the molar ratio of said transition metal ofsaid catalyst to said alkylaluminium is in the range of 1:1˜1:3000. 23.The catalyst system of claim 22 wherein said molar ratio is from about1:50 to about 1:1000.